Piperidine derivatives

ABSTRACT

New piperidine derivatives of 1,3-pyrimidine and 1,3,5-triazine are used as stabilisers for organic materials, especially for polymers.

Chalmers et al.

PIPERIDINE DERIVATIVES Inventors: Alexander Michael Chalmers,

Cheadle Hulme; James Jack, Bramhall; Barry Cook, Manchester,

Appl No: 350,296

Foreign Application Priority Data Apr. 2], I972 United Kingdom [8558/72Feb. 3, [973 United Kingdom 5469/73 US. Cl.,.... 260/248 CS; 260/2495;260/2498; 260/249.6; 260/458 N; 260/2564 C; 260/2564 R; 260/2565 R lnt.Cl. C07D 251/26 Dec. 9, 1975 [58] Field of Search 7, 260/248 CS, 2496,249.5, 260/2498 [56] References Cited UNITED STATES PATENTS 3,156,68911/1964 Dexter et a] 260/2498 X 3,156,690 1 [/1964 Dexter et a] 260/2498X 3,734,883 5/1973 Holt 260/458 N FOREIGN PATENTS OR APPLICATIONS2,227,689 l2/l972 German Primary Examiner-John M. Ford Attorney, Agent,or FirmNest0r W. Shust [57] ABSTRACT New piperidine derivatives ofLES-pyrimidine and 1,3,5-lriazine are used as stabilisers for organicmaterials, especially for polymers.

ll Claims, N0 Drawings PIPERIDINE DERIVATIVES The present inventionrelates to new compounds useful as stabilisers for organic material andin particular to new piperidine derivatives useful for the stabilisationof polymers.

in British Pat. Specification No. 977,587 there are described compoundshaving the formula:

and salts thereof, wherein U is CH or N and Z is a residue having theformula wherein R and R, are the same or different and each is astraightor branched alkyl residue having from I to 12 carbon atoms, orR, and R, form, together with the 2 residue, wherein R is hydrogen, astraight or branched alkyl residue having from i to 20 carbon atoms oran aralkyl residue having from 7 to 12 carbon atoms; Y is 0, hydrogen, astraight or branched alkyl residue having from I to 20 carbon atoms, analkenyl or alkynyl residue having from 3 to 12 carbon atoms, an aralkylresidue having from 7 to l2 carbon atoms or the group wherein R ishydrogen, or a methyl or phenyl residue; n is 0 or I; and A is CH,-, orthe group wherein R, is hydrogen or an alkyl residue having from i to 20carbon atoms; 2' and Z' are the same or different and each is apiperidine residue of formula ll as hereinbefore defined, a halogenatom, a substituted amino group having the formula:-

wherein R and R are the same or different and each is hydrogen, astraightor branched alkyl residue having from I to 20 carbon atoms, acycloalkyl residue having from 5 to 12 carbon atoms, an aryl residuewhich is unsubstituted or substituted by one or more alkyl groups andhaving a total of from 6 to 18 carbon atoms or an aralkyl residue havingfrom 7 to 12 carbon atoms; or R and R together with the nitrogen atom towhich they are bound form a heterocyclic residue having 5 to 7 ringatoms; or Z" and Z' are an hydroxy or ether group having the formula:-

oR. IV wherein R, is hydrogen, a straightor branchedchain alkyl residuehaving from 1 to 20 carbon atoms, a cycloalkyl residue having from 5 to12 carbon atoms, an aryl residue which may be unsubstituted orsubstituted by one or more alkyl groups, having a total of 6 to 18carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms; orZ" and Z' are a thiol or thio ether group having the formula:

, V wherein R6 is hydrogen, a straightor branched alkyl residue havingfrom 1 to 20 carbon atoms, a cycloalkyl, having from 5 to 12 carbonatoms or a phenyl or benzyl residue.

Preferably, the ring atom U is -N.

Examples of alkyl substituents R, and R, include methyl, ethyl,n-propyl, isopropyl, n-butyl, secbutyl, nhexyl, n-octyl and n-dodecylresidues; however, preferred alkyl residues R, and R, are those havingfrom 1 to 4 carbon atoms and most preferably R, and R are each a methylresidue.

When the residue R, and R together with the carbon atom to which theyare bound, form a cycloalkyl group, examples of such cycloalkyl groupsare those of formula:

CH a

Examples of the residue X are O, S, -NH- and NR, wherein R, is a methyl,ethyl, isobutyl, nhexyl, n-decyl, n-eicosyl or benzyl residue.Preferably, however, X is O- or NH.

Examples of Y, apart from hydrogen and O, are methyl, ethyl, n'propyl,isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl, n-dodecyl, allyl,a-methallyl, lundecenyl, prop-2-ynyl, benzyl, a-methylbenzyl,pmethylbenzyl, p-methyl-a-methylbenzyl, a-naphthylmethyl andB-hydroxyethyl, B-hydroxypropyl or B- hydroxy-fi-phenyl ethyl residues.Particularly preferred substitutent Y however are hydrogen and straightor branched alkyl residues having from I to 4 carbon atoms, the mostpreferred substituents being hydrogen and methyl residues.

Examples of residue A when n is l are CH,, and

wherein R, is hydrogen, a methyl, ethylpisopropyl, secbutyl, n-hexyl,n-decyl or n-eicosyl residue. Preferably R, is hydrogen and preferably,either n is 0 or n is l and A is -CH,CH,-.

A particular sub-group of Z" and/or 2' are substituted amine groups-NkR, wherein examples of substituents R, and R apart from hydrogen, aremethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl,n-octyl, n-dodecyl, n-eicosyl, cyclopentyl, cyclohexyl, cyclododecyl,p-methylphenyl, p-t-butylphenyl, p-ndodecylphenyl, benzyl,a-methylbenzyl and a-naphthylmethyl residues; substituents R, and R are,however, preferably hydrogen or an alkyl residue having from 6 to carbonatoms.

when the residues R, and R, together with the nitrogen atom to whichthey are bound form a heterocyclic residue, the heterocycle may containfurther heteroatoms such as a further nitrogen atom or an oxygen atom towhich they are bound. Examples of such heterocyclic residues arepyrrolidin-l-yl, piperidino, Z-methylpiperidino, 4-n-hexylpiperidino,morpholino, piperazin-l-yl, 2-methylhexahydroazepin-l-yl; preferredheterocyclic residues, however, are morpholino and piperidino residues.

Examples of substituent R apart from hydrogen, are methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl, n-dodecyl,n-eicosyl, cyclopentyl, cyclohexyl, cyclododecyl, phenyl,p-rnethylphenyl, tbutylphenyl, p-n-dodecylphenyl, benzyl,a-methylbenzyl, p-methyl-a-methylbenzyl and a-naphthylmethyl residues;substituent R is, however, preferably an alkyl group having from 6 to 20carbon atoms.

Examples of substituent R,,, apart from hydrogen, are methyl, ethyl,n-propyl, isopropyl, n-butyl, secbutyl, nhexyl, n-octyl, n-dodecyl,n-eicosyl, cyclopentyl, cyclohexyl, cyclododecyl, phenyl and benzyl. Thepreferred substituent R is an alkyl residue having from 6 to 20 carbonatoms.

Preferably, Z" and Z' are each the same or different piperidine residuell. In less preferred embodiments, Z" and/or 2'' are halogen, preferablychlorine, N-alkyl substituents or S-alkyl substituents.

The invention also includes salts of the compounds of formula I forinstance salts of inorganic acids such as phosphates, carbonates,sulphates and chlorides and salts of organic acids such as acetates,stearates, maleates, citrates, tartrates, oxalates, benzoates andsubstituted carbamic acids.

A preferred sub-group of compounds are those having the formula:-

wherein D, D" and D"' are the same or different and each is halogen or aresidue of formula:-

1 RI] g a wherein R,'and R, are the same or different and each is astraight or branched allryl residue having from 1 to 12 carbon atoms, orR, and R together with the carbon atom to which they are bound, form acycloalkyl residue having from 5 to 12 carbon atoms, X is an -O, -S orNR-, residue wherein R, is hydrogen, an alkyl residue having from 1 to12 carbon atoms or an aralkyl residue having from 7 to 12 carbon atoms,Y is 0, hydrogen, an alkyl residue having from I to 12 carbon atoms, analkenyl or alkynyl residue having from 3 to 12 carbon atoms, an aralkylresidue having from 7 to 12 carbon atoms or the group:

3 ,925 ,3 76 6 1- 6-chloro-2,4-bis[2',2',6',6'-tetramethylpiperidinyli4-amino]-1,3-pyrimidine 6-chloro-2,6-bis[ l'-ethyl-2',2',6,6-tetramethyly 5 piperidinyl-4'-amino]-l ,3-pyrimidinewherein R IS hydrogen, or a methyl or phenyl residue, 4 1 2 2'3 z w i-4' n is O or l and A' is CH:, or aminoLlJTw-imidine2-methylamino-4,6-bis[2',2',6',6'-tetramethylpiperidinyl-4'-amino]-l,3,5-triazinei m 2-ethylamino-4,6-bis[2,2',6,6'-tetramethylpiperidinyl-4'-amino]-l ,3,S-triazine 2-iso-propylamino-4,6bis[ 2',2',6',6'-tetramethylwherein Ris hydrogen or an alkyl residue having from P P Y ll to 12 carbon atoms;with the proviso that at least one 2 n-heXylaminO 46 biS[2',2"6"6tetramethy]' of D, D" and D' is not a halogen atom; and salts of 15 P py l- ,3i5-triflline these compounds.2-n-octydecylamino-4,6-bis[2',2',6',6-tetramethyl- Within the group ofcompounds'of formula IA, these p p y 1- ,3.5-U'iaZin6 compounds arepreferred wherein D, D" and D" are 2-cyclopentylamino-4.fiy the same ordifferent piperidine residue of formula HA. p p y l .3.5-lrialil1e Morepreferably, residues D, D" and D are the same -y y i y piperidineresidue llA. It is also preferred that X is P P Y lor n is 0 RI and R2are each a methyl 2-cyclododecylamino-4,6-bis[2',2',6,6'-tetrameresidueand Y is hydrogen or an alkyl residue having y P P y li from 1 to 4carbon atoms, especially a methyl residue. y 1 y A further sub-group ofpreferred compounds of for- P P y ,3i5'il'ialine mula l are those offormula; Z-ethyl-n-propylamino-4,6-bis[2',2,6',6'-tetrameg I u c A ailCH3 R o N O In an R wherein R," and R are the same or different andthylpiperidinyl-4'-amino]-l,3,S-triazine each is a straightorbranched-chain alkyl group having2-methyl-n-decylarnino-4,6-bis[2',2',6,6'-tetramefrom 1 to 12 carbonatoms or R," and R,", together thylpiperidinyl-4-amino]-l,3,5-triazinewith the carbon atom to which they are each bound,2-anilino-4,6-bis[2',2',6,6'-tetramethylpiperidinylform a cycloalkylresidue having from 5 to 12 carbon 4-amin0]-I,3,5-triazine atoms, and Y"is hydrogen, a straightor branched-2-(p-t-butylanilino)-4,6-bis[2,2',6,6'-tetramethylchain alkyl grouphaving from I to 12 carbon atoms, an i ridi l-4'-amino]-l ,3,5-rriazinealkenyl group having from 3 to 12 carbon atoms or an2-(p-methylanilino)-4,6-bis[2',2',6',6-tetramethylaralkyl group havingfrom 7 to 12 carbon atoms; and i idi l-4-amin ]-1,3,5-triazine salts ofthese compounds. 2-(p-n-dodecylanilino)-4,6-bis[2',2',6',6-tetrameit ispreferred that substituents Rf, R," and each a i i i mu i 1. ,3,5- i imethyl residue and that Y" is hydrogen or a lower alkyl 2 i 4 2' 2', h1- residue, especially a methyl residue. i ridin l-4'-amino]-l,3,5-triazine Specific examples of compounds of formula I ing h 4 2"2'5' elude: ramethylpiperidinyl-4'-amino]-l ,3,5-triazine 3 3 y p p y2-amino-4,6-bis[2,2',6',6'-tetramethylpiperidinylamino]- 1 ,B-pyrimidine4'-amino 1-1 ,3,S-triazine l "P y p p2-hydroxy-4,6-bis[2,2',6,6'-tetramethylpiperidinylamino]-1.3-pyrimidin4'-amino 1-1 ,3 ,S-triazine 1 1 2,4-Dichloro-6-( l',2',2',6,6'-pentamentyl piperidinyl-4'-oxy l ,3 ,S-triazine2,4-Dichloro-6-( l 'oxyl-Z',2,6,6-tetramethylpiperidinyl-4-oxy)-1,3,5-triazine 2,4-Dichloro-6-(2',2',6',6'-tetramcthyl piperidinyl- 4-ethylenoxy)-l ,3,S-triazine 2,4-Dich|oro-6-( 2',2',6,6'-tetramethyl piperidinyl- 4'-ethylenamino)-l,3,5-triazine 2,4-Dichloro-6-(2'2',6',6-tetra methyl piperidinyl-4'-methylenoxy )-l ,3 ,5 -triazine 2,4-Dichloro-6-(2',2',6',6'-tetramethyl piperidinyl- 4'-methylen amino)l ,3,5-triazine 2,4,6Tris[ l-/3-hydroxyethyl-2',2',6,6'-tetramethylpiperidinyl-4'-oxy]1,3,5-triazine2,4,6-Tris[ l '-B-hydroxyethyl-2',2',6,6'-tetramethylpiperidinyl-4 amino]-1 ,3 ,S-triazine 2,4,6-Tris[ l-B-hydroxuethyl-2',2',6',6'-tetramethylpiperidinyl-4-ethyleneaminol'l,3,5-triazine 2,4,6Tris[ l-[3-hydroxypropyl-2',2',6',6'-tetramethylpiperidinyl-4'-oxy]-l,3,5-triazine 2,4,6-Tris[l-B-hydroxypropyl-2,2',6,6'-tetramethylpiperidinyl-4'-amino]-l,3,5-triazine 2,4,6Tris[ l '-B-hydroxy-B-phenylethyl-Z',2',6',6-tetramethylpiperidinyl-4'-oxy]-l ,3 ,S-triazine 2,4,6-Tris[ l'-B-hydroxy-B-phenylethyl-Z',2',6',6- tetramethylpiperidinyl-4'-amino]-l,3 ,S-triazine as well as the sulphate, chloride, oxalate and acetatesalts of the preceding compounds 1A.

Specific examples of compounds of formula lB include:

2,4,6-tris[2',2',6',6-tetramethylpiperidinyl-4'-oxy]- 1,3 ,S-triazine2,4,6-tris[2',2'-dimethyl-6',6-diethylpiperidinyl-4'-oxy]-l,3,5-triazine 2,4,6-tris[2',2',6'-trimethyl-6-ethylpiperidinyl-4-oxy l ,3 ,S-triazine2,4.6-tris[2'.2'-dimethyl-6,6-diisopropylpiperidinyl-4 -oxy]-l ,3.5-triazine2,4,6tris[2',2'-dimethyl-6',6-di-n-dodecylpiperidinyl-4'-oxy]-1,3,5-triazine2,4-bis[2,2,6',6-tetramethylpiperidinyl-4'-oxy1-6- l "-aza-2",2''-dimethylspiro{ 5,5 ]-undecane-4"-oxy]- l,3,5-triazine 2,4,6-tris[ l,2',2',6,6'-pentamethylpiperidinyl-4'- oxyll ,3,5-triazine 2,4,6-tris[ l'-ethyl-2,2,6',6'-tetramethylpiperidinyl- 4'-oxyl-l,3,5-triazine2,4,6-tris[ l '-n-butyl-2',2',6',6'-tetramethylpiperidinyl-4'-oxy]- l,3,5-triazine 2,4,6-tris[ l '-n-dodecyl-2',2',6',6'-tetramethyl'piperidinyl-4'-oxy]-l ,3 ,S-triazine 2,4,6-tris[ l'-allyl-2,2,6',6'-tetramethylpiperidinyl- 4'-oxy I ,3 ,S-triazine2,4,6-tris[ l -benzyl-2,2,6',6-tetramethylpiperidinyl-4'-oxy]-l,3,5-triazine 2,4,6-tris[ l '-azal '-benzyl-2,2'-dimethylspiro-[ 5,5undecane-4'-oxy]- l ,3 ,S-triazine spiro-[ 5,5 ]-undec- 122,4-bis[2',2',6,6-tetramethylpiperidinyl-4"oxy)-6- l",2",2",6",6"-pentamethyl piperidinyl-4"- oxy] 1,3 ,S-triazine2-[2',2,6',6'-tetramethylpiperidinyl-4'-oxy]-4,6- bis[ 1",2",2",6",6"-pentamethyl piperidinyl-4"-oxy]- l ,3,5'triazine.

The present invention also provides a first process for the productionof a compound of formula 1 comprising reacting a halogenatedl,3,5-triazine or a halogenated pyrimidine preferably a cyanuric halide,especially cyanuric chloride, with the compound having the formula:

CH1: s

Ig-Y (v1) R is; 1

In formula I wherein U is N and wherein Z" and Z' are piperidineresidues, the compounds of formula 1 may be symmetrical orunsymmetrical, depending upon the nature of the substituents in theformula VI. For the preparation of symmetrical compounds of formula I,it is convenient to use at least three molecular proportions of thecompound of formula VI per molecular proportion of cyanuric halide,preferably cyanuric chloride.

In order to produce an unsymmetrical compound of formula I, dissimilarcompounds of formula VI may be added stepwise by introducing one or tworesidues into the triazine molecule at one time. In this way, two orthree different piperidinyl residues may be introduced into the triazinenucleus.

For the preparation of compounds having two identical piperidineresidues, the reaction is carried out using at least two molecularproportions of a single compound Vl per molecular proportion of cyanurichalide. it is convenient to carry out the reaction in the presence of ahalogen acid binding agent and optionally in the presence of a solventinert under the reaction conditions. Suitable examples of halogen acidbinding agents include organic bases such as triethylamine, inorganicbases such as sodium hydroxide or sodium carbonate; alternatively anexcess amount of the amine reactant of formula VI may be employed as thehalogen binding agent. if a solvent is used suitable examples of suchsolvents are toluene and xylene.

In the particular case of compounds of formula VI wherein X is -O, thealkali metal salt of the compound may be first prepared, for instance,by reacting the compound with an alkali metal, prior to reaction withthe cyanuric halide.

When Z" and Z' are not both piperidine residues, reaction of theremaining halogen can be accomplished by treating the derived compoundwith an amine of formula:

or the derived strong acid salt an alcohol of formula:

Holt, Vlll or a thio compound of formula:

HSR, IX

The reaction is conveniently carried out in the presence of a suitablehalogen acid binding agent as described above. In the particular case ofthe amine Vii an excess amount of this reactant may be employed. ln theparticular case of the alcohol Vlll the alkali metal salt may first beprepared prior to reaction.

Alternatively these compounds containing two piperidine residues can beprepared by reacting a cyanuric halioe firstly with one molecularproportion of the compounds Vll, Vlll and [X and then by treating thederived dihalogenated material with the piperidine compound VI using theconditions described above.

For compounds containing only one piperidine residue, one molecularproportion of compound Vl may be added, usually at low temperature, tothe cyanuric halide using the conditions described above. The deriveddihalogenated material can then be treated with one or two molecularproportions of VII, VIII or [X as desired.

Alternatively one or two molecular proportions of the compounds Vll,Vlll or D( may be added to one molecular proportions of a cyanurichalide to yield the dior monohalogenated product which can then bereacted with one molecular proportion of piperidine compound VI.

The present invention also provides a second process for producing acompound of formula l wherein Y is other than hydrogen, comprisingreacting the corresponding compound of formula l wherein Y is hydrogenwith a compound capable of replacing the hydrogen at the nitrogen atomby the group Y.

For example, the nitrogen substitution reactions may be effected usingan alkylating, alkenylating, alkynylating or aralkylating agent such asalkyl, alkenyl, alkynyl or aralkyl halide.

Alternatively, the nitrogen substitution reactions may be carried out bya Leuckart or Wailach reaction using formic acid and the appropriatealdehyde or ketone. For example, the corresponding NH compound may bereacted with formic acid and formaldehyde to produce the N-methylcompound.

To produce a compound of formula I wherein one or more of thesubstituents Y is a hydroxyalkyl group, the corresponding compound offormula i wherein Y is hydrogen, may be reacted with the appropriatealicylene oxide such as ethylene oxide, propylene oxide or styreneoxide.

To produce a compound of formula I wherein one or more of Y is O, thecorresponding compound of formula I wherein the corresponding Ysubstituent is hydrogen may be oxidised with a peroxide, such ashydrogen peroxide, optionally in the presence of pertungstic acid, orwith a per-acid such as performic or peracetic acid. in a modificationof this oxidation reaction, the starting-material may be thecorresponding N-lower alkyl compound rather than the NH compound offormula 1.

Although in theory this method may be used to produce compounds offormula I in which only one of Y is O, in practice it is very muchpreferred to conduct the oxidation so that all of Y are otherwisecomplex mixtures are obtained from which it is difficult to isolatepartial N-oxyls of formula I.

It is to be understood that the above processes can' also be used toproduce the less preferred compounds of formula I wherein U is CH. Thecompounds of formula I have been found to be excellent light stabilisersfor organic material, especially polymers. Accordingly, the presentinvention also provides a composition comprising an organic materialand, as stabiliser, a

minor proportion of a compound of formula I as hereinbefore defined.

Compounds of formula l have been found to impart to polyolefines anexceptionally high degree of stability towards deterioration normallyinduced by the effects of ultra-violet radiation or exposure to heat.Moreover, this improved stability is achieved without affecting thecolour properties of the treated polyolefine. The stabilisers of theinvention provide effective light and/or heat stabilisation, especiallyfor lowand high-density polyethylene and polypropylene and polystyreneas well as polymers of butene-l pentene-i, B-methylbutene-l hexene-l4-methylpentene'l 4-methylhexenel and 4,4-dimethyl-pentene-l, and alsocoand terpolymers of olefines, particularly of ethylene or propy lene.

Other organic materials susceptible to degradation by the effects oflight and the properties of which are improved by the incorporationtherein of a compound of Formula I include natural and syntheticpolymeric materials, for instance natural and synthetic rubbers thelatter including, for example, homo-, coand terpolymers ofacrylonitrile, butadiene and styrene.

Specific synthetic polymers include polyvinyl chloride, polyvinylidenechloride and vinyl chloride co polymers, polyvinyl acetate as well ascondensatior polymers derived from ether, eseter (derived from carboxylic sulphonic or carbonic acids), amide or ure thane groupings.These polymers can, for instance form the basis of surface coating mediasuch as paint: and lacquers having an oil or resin, for instance aralkyd or polyamide resin base. i The amount of the compound of formula Iwhich i: incorporated into the organic material in order tt achievemaximal protection against degradation b light varies according to theproperties of the organit material treated and according to the severityof tin light radiation and to the length of exposure. However for mostpurposes it is sufficient to use an amount 0 the compound of formula 1within the range of fron 0.01 to 5% by weight, more preferably withinthe rang of from 0.1 to 2% by weight based on the weight of un treatedorganic material.

The compounds of formula I may be incorporate into the polymericmaterial by any of the known tech niques for compounding additives witha polymer. Fo example, the compound of formula 1 and the polyme may becompounded in an internal mixer. Alterna tively, the compound of formulamay be added as a sc lution or slurry in a suitable solvent ordispersant, fo instance an inert organic solvent such as methanol, etianol or acetone to powdered polymer and the whol mixed intimately in amixer, and the solvent subse quently removed. As a further alternativethe con pound of formula I may be added to the polymer durin thepreparation of the latter, for instance at the late stage of polymerproduction, to provide pre-stabilise polymer material.

Optionally, the composition of the invention ma contain one or morefurther additives, especially thos used in polymer formulations, such asantioxidants r the phenol or amine type, UV. absorbers and light pritectants, phosphite stabilisers, peroxide decomposer polyamidestabilisers, basic co-stabilisers, polyvin chloride stabilisers,nucleation agents, plasticizers, ll bricants, emulsifiers, anti-staticagents, flame-protec ants, pigments, carbon black asbestos, glassfibres, ka' lin and talc.

The present invention therefore includes binary. tertiary andmulti-component decompositions containing the stabiliser of formula Itogether with one or more functional additives for polymers.

Examples of suitable antioxidants are those of the hindered phenol typesuch as those selected from the following groups:

1. Phenolic compounds having the general formula lllustrative examplesof such compounds are: 4 ,4'-thiobis-( 2-t-butyl-5 -methylphenol)4,4-thiobis-( 2-t-butyl-6-methylphenol)2,2-thiobis-(6-t-butyl-4-methylphenol)4,4'-thiobis-(Z-methyI-S-t-butylphenol) 6. Phenolic compounds having theformula lllustrative examples of such compounds are: octadecyl-( 3,5-dimethyl-4-hyd roxybenzylthio )-acetate dodel5 cyl-(3,5-di-t-butyl-4-hydroxybenzylthio)-propionate Q( H=l. wherein Q is A. iscmcooR"),

illustrative examples of the compounds shown above are2,6-di-t-butyl-p-cresol 2-methyl-4,6-di-t-butylphenol and the like2,-di-octadecyl-p-cresol 3. Phenolic compounds having the formula:

lllustrative examples of the compounds shown are:2,2-methylene-bis(6-t-butyl-4-methylphenol)2,2'-methylene-bis(6-t-butyl-4-ethylphenol)4,4-butylidene-bis(2,6-di-t-butylphenol) 4,4'-( Z-butylidene )-bis(Z-t-butyl-S-methylphenol) 2,2 '-methylene-bis[6(2-t-methylcyclohexyl)-4- methylphenol]2,2'-methylene-bis(B-t-butyLS-ethylphenol) 4,4 '-methylene-bis( 3,S-di-t-butylphenol) 4,4-methylene-bis(3-t-butyl-5-methylphenol)2,2'-methylene-bis(3-t-butyl-5-methylphenol) the like. 4. Phenoliccompounds having the formula:

and

lllustrative examples of such compounds are: 2,S-di-t-butylhydroquinone2,6-di-t-butylhydroquinone 2,5-di-t-butyl-4-hydroxyanisole 5. Phenoliccompounds having the formula:

7. Phenolic compounds having the formula wherein T is hydrogen R or Q asdefined above.

lllustrative examples of such compounds are:

l ,1,3-tris(3,5-dimethyl-4-hydroxyphenyl)-propane l, l,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)- butane 1,1,5 ,5 -tetrakis-(3 '-t-butyl-4'-hydroxy-6-methylphenyl)-n-pentane 8. Phenolic compoundshaving the formula:

'1 CH CH 2 Q 0 cn e 3 CH3 CHZB wherein B, B and l? are hydrogen, methylor 0. provided that when B and B are 0 then B is hydrogen or methyl andwhen B is Q then B and I? are hydrogen or methyl.

Illustrative examples of such compounds are:

l,4-di(3 ,5-di-t-butyl-4-hydroxybenzyl)-2,3 ,5 ,6-tetramethylbenzenel,3,5-tri( 3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-

trimethylbenzene 9. Phenolic compounds having the formula (Q) M H D isalkyl group having from 6 12 carbon atoms or illustrative examples ofsuch compounds are:

2,4-bis-(n-octylthio)6-(3,5-di-t-butyl-4-hydroxyaniline)-l ,3,S-triazine6-(4-hydroxy-3-methyl-5t-butylanilino)-2,4-bis-(noctyl-thio)-l,3,5-triazine 1,6-n-hexanediol-bisl 3 ,5 '-di-t-butyl-4-hydroxyphenyl)propionatel l2. Phenolic compounds having the formula where .x is aninteger of l or 2.

illustrative examples of such compounds are Di-n-octadecyl3,S-di-t-butyl-4-hydroxybenzyl-phosphonate Di-n-octadecyl3-t-butyl-4-hydroxy-5-methylbenzylphosphonate Di-n-octadecyll-(3,5-di-t-butyl-4-hydroxyphenyl)el3. Phenolic compounds having theformula wherein W and Q are defined above.

Illustrative examples of such compounds are:

tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanuratetris-(3-t-butyl-4-hydroxy-5-methylbenzyl)isocyanurate. The abovephenolic hydrocarbon stabilizers are known and many are commerciallyavailable.

While any of the above mentioned antioxidants can be useful incombination with the ultraviolet light stabilizers of this invention,the preferred antioxidants consist of the hindered phenols in groups I,8, 9, l0, 1 l, 12 and 13 as mentioned above. The most preferred hinderedphenols are those of groups 1, 9, ll, 12 and 13.

Further examples of antioxidants are those of the aminoaryl series forinstance aniline and naphthylamine derivatives as well as theirheterocyclic derivatives such as:

phenyll -naphthylamine phenyI-Z-naphthylamine N ,N'-diphenyl-p-phenyldiamine N,N'-di-sec.butyl-p-phenylenediamine6-Ethoxy-2,2,4-trimethyl-l ,Z-dihydroquinoline6-Dodecyl-2,2,4-trimethyl-1,Z-dihydroquinoline Monoanddi-octyliminodibenzyl and polymerised 2,2,4-trimethyl-l,2-dihydroquinoline.

Ultraviolet absorbers and light protectants include a.2-(2'-hydroxyphenyl)benzotriazoles, for instance -methyl;3',5'-di-t-butyl; 5'-t-butyl; 5-chloro-3',5 '-dit-butyl;S-chloro-3'-t-butyl-5'-methyl; 3'-sec. butyl-5'- tert.butyl;3'-[a-methylbenzyl]-5'-methyl-; 3'-[amethylbenzyl)-5'-methyl-5-chloro-;4-octoxy-; 3,5'-

di-t-amyl; 3'-methyl-5-carbamethoxyethyl; S-chloro- 3',5'-di-tamylderivatives.

b. 2,4-bis-(2'-hydroxyphenyl)-6-alkyl-S-triazines, for instance the6-ethyl or 6-undecyl derivatives.

c. Z-hydroxybenzophenones, for instance the 4- hydroxy, 4-methoxy,4-0ctoxy-, 4-decyloxy-, 4- dodecyloxy-, 4,2, 4'-trihydroxy or2'-hydroxy-4,4'- dimethoxy derivatives.

d. l,3-Bis(2'-hydroxybenzoyl)-benzenes for instance, l,3-bis-(2'-hydroxy-4'-hexyloxybenzoyl)benzene 1,3-bis-(2'-hydroxy-4'-octoxybenzoyl)benzene l,3-bis-(2'-hydroxy-4'-dodecyloxybenzoyl)benzene e. Aryl esters from optionallysubstituted benzoic acids such as phenylsalicylate,octylphenylsalicylate, dibenzoyl resorcinol, bis-(4-tert.butylbenzoyl)resorcinol, benzoylresorcinol and 3,5-di-tert.butyl-4-hydroxybenzoicacid-2,4-di-tert.butyl phenyl ester and -octadecyl ester and-2-methyl-4,6-di-tert.butyl phenyl ester.

f. Acrylates, for instance aCyano-B,B-diphenylacrylic acid ethyloriso-octyl ester, a-carbomethoxy-cinnamic acid, methylor butyl ester andN-(B-carbomethoxyvinyl)-2-methyl indoline.

g. Nickel compounds such as nickel complexes of2,2-thio-bis-(4-tert.octylphenol), for instance the lzl and I12complexes, optionally having other ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine; nickel complexes ofbis-(4-tert.octylphenyl) sulphone such as the 2:] complex, optionallyhaving other ligands such as 2-ethylcarproic acid; nickel dibutyldithiocarbamates; nickel salts of 4- hydroxy-3,5-cli-tert.butylbenzyl-phosphonic acid mono-alkyl esters such as the methyl-,ethylor butyl esters; the nickel complex of2-hydroxy-4-methyl-phenyl-undecylketonoxime; anclnickel-3,5di-tert.butyl-4- hydroxy benzoate, and

h. Oxalic acid diamides, for instanc 4,4'-dioctyloxyoxanilide 2 ,2'-dioctyloxy-5 ,5 '-di-tert.butyl-oxanilide 2,2'-di-dodecyloxy-S,5'-di-tert.butyl oxanilide Z-ethoxy-S-tertiarybutyl-2'-ethyl-oxanilide2-ethoxy-2'-ethyl-oxanilide mixtures of oand p-methoxy andethoxy-di-substituted oxanilides and the compound of formula:

CH CH;

Phosphite stabilisers include triphenyl phosphite, diphenylalkylphosphites, phenyl dialkyl phosphites, trinonylphenyl phosphite,trilauryl phosphite, trioctadecyl phosphite,3,9-di-isodecyloxy-2,4,8,l0-tetraoxa- 3,9-diphosphaspiro-(S,5)-undecaneand tri-(4- hydroxy-3 ,5-di-tert.butylpheny1)phosphite.

Peroxide-decomposing compounds for polyolefins include esters ofB-thiodipropionic acids, for instance the lauryl-, stearyl-, myristylortridecyl esters, salts of mercaptobenzimidazoles such as the zinc saltand diphenylthiourea.

Suitable polyarnide stabilisers include copper salts in combination withiodides and/or further phosphorus compounds and salts of bivalentmanganese.

Basic co-stabilisers are, for example, polyvinylpyrrolidone, melamine,benzoguanamine, triallyl cyanurate, dicyandiamide, urea derivatives,hydrazine derivatives, amines, polyamides, polyurethanes, alkali andalkaline earth salts of higher saturated or unsaturated fatty acids suchas calcium stearate.

Polyvinyl chloride stabilizers include organotin compounds, organo leadcompounds and Ba/Cd salts of fatty acids.

Examples of nucleation agents are 4-tert.butyl benzoic acid, adipic acidand diphenylacetic acid.

As with the compound of formula 1, any further additive isadvantageously employed in a proportion within the range of from 0.01 toby weight, based on the weight of untreated polymeric material.

In binary combinations with one or more antioxidants listed above or intertiary combinations with such antioxidants and UV. absorbers listedabove, the compounds of formula I provide very effective stabilizerpackages in polyolefine formulations.

The halo-compounds of formula 1, in addition to their property offunctioning as a stabiliser for organic material, may also find use asintermediates for materials such as other stabilisers.

Some Examples will now be given. Parts and percentages are by weightunless otherwise stated.

EXAMPLE 1 To 28.2 parts of 2,2,6,6-tetramethylpiperidin-4-ol in 200parts of dry xylene were added in portions 4.2 parts of sodium. Thismixture was heated at reflux for 18 hours and then cooled. 10.1 parts ofcyanuric chloride were added in portions and the mixture brought to areflux temperature for 1 hour. Evaporation to dryness under reducedpressure was followed by extraction with petroleum ether (b.p. 6080C.)using a Soxhlet extractor apparatus. Evaporation vacuo gave the desiredproduct contaminated with 2,2,6,6-tetramethylpiperidin-4-ol. Sublimationin vacuo removed this contaminant and the residual colourless solid wascrystallised from petroleum ether (b.p. 6080C.) to yield 23.7 parts of2,4,6-tris[2',2',6,6'-tetramethylpiperidinyl-4'-oxy]-l ,3,5-triazine ofmelting point 198-200C. This material gave the following elementalanalysis by weight:

Required for C H MO; Found Carbon 65.90% 65.72%

Hydrogen 9.95% 9.85%

Nitrogen 15.37% 15.19%

EXAMPLE 2 38 parts of polypropylene were homogenised with 0.76 part ofn-octadecyl-B-(4'-hydroxy-3,5'-di-t-butylphenyl) propionate in akneading machine over a period of 3 minutes. 0.19 part of the product ofExample 1 was then added and homogenisation continued for another 7minutes.

The homogenised mixture was removed from the kneader and pressed to athickness of from 2 to 3 mm. in a press.

9 parts of the polypropylene mixture were then charged into a secondpress in which the press-plates were protected by aluminum foil having athickness of 0.1 mm. The press was closed and, for 2 minutes, nopressure was applied. The pressure was then increased up to a maximum of12 tons and this pressure held for 6 minutes, the temperature of thepress being 260C. The pressure was released and the material (0.3 mmthick) was cooled under running water.

This material was cut into from 3 to 5 pieces of 35 X 35 mm section andre-charged to the press. The press was closed and no pressure wasapplied for 2 minutes.

Over another 2 minutes the pressure was increased to 8 tons, the presstemperature being 260C. This pressure was maintained for 2 minutes andthen the pressure released. The polypropylene foil of 0.1 mm thicknesswas removed and tempered immediately in a circulating air ovenmaintained at 150C. over a period of 60 minutes.

A section measuring 44 X mm was separated from the 0.1 mm temperedpolypropylene foil and exposed to light irradiation in a fademeterdevice consisting of a circular bank of 28 alternate sunlight andblacklight lamps. The sunlight lamps were 2 feet long, 20-wattfluorescent lamps characterised by a peak emission of 3,000 Angstromunits; the blacklight lamps were 2 feet long, 40-watt ultraviolet lampscharacter ised by a peak emission of 3,500 Angstrom units. The samplewas rotated concentrically about the bank of lamps so that the radiationtherefrom was uniformly distributed over the section under test.

The exposed sample was examined periodically and the time at which thesample reached 50% of the initial elongation was noted.

Table 1 Time to reach 50% Example Additive initial elongation (hours)None (control) 2 2,4,6-tris[2,2'.6',6'- 625 tetramethylpiperidinyM'-oxy]-1,3 ,S-triazinc EXAMPLE 3 230/265I275C. 270C.

400 m./minute 1 5 /137 denier 6 g./denier Extruder temperatures Melttemperature at the dye Spinning Speed Stretching Ratio Titer ofMultifilament Tensile Strength The multifilament obtained was mounted ona sample holder of a Xenotest apparatus (Quarzlampen Gmbl-l) using whitecardboard as backing. ln intervals of 200 hours of exposure time, 5fibre samples are measured for their retained tensile strength. The dataobtained are plotted against exposure time and the exposure time to give50% loss of original tensile strength is derived from the graph. Thisvalue is taken as the failure time.

The data are shown in the following Table 11 which also includes datarelating to a control experiment omitting the product of Example 1.

Table ll-continued Time to Example Additive failure (hours) 32,4.6-tris[2.2',6',6'-tetra- 1750 methyl piperidinyl-4-oxy]1,3.5-triazine EXAMPLE 4 18.5 Parts of cyanuric chloride were slurriedin 600 parts of water and treated with 31.4 parts of 4-amino-2,2,6,6-tetramethylpiperidine. 8 Parts of sodium hydroxide in parts ofwater were then carefully added and the suspension stirred at roomtemperature for thirty minutes. The suspension was then heated at 90Cfor 16 hours and allowed to cool. 39.5 Parts of a colourless solid,2-ch1oro-4,6-bis-(2',2',6',6'-tetramethylpiperidinyl-4'-amino)-l,3,5-triazine were separated by filtration, washed with water anddried in vacuo. This material of melting point 277278C, showed thefollowing elemental analysis by weight:

Carbon 59.32% 59.54%

Hydrogen 9.25% 9.09%

Nitrogen 23.06% 22.89%

Chlorine 8.36% 8.32%

EXAMPLE 5 12 Parts of the material obtained in Example 4 were warmed ina solution comprising 920 parts of ethanol and 190 parts of water. 9Parts of 4-amino-2,2,6,6-tetramethylpiperidine were added and thesolution heated at reflux for 16 hours. The solution was then evaporatedto dryness and treated with 200 parts of water. Filtration afforded 14.0parts of a colourless solid 2,4,6-tris[2,2',6',6'-tetramethylpiperidinyl-4'- amino] 1 ,3,5-triazine monohydrate which was purified bySoxhlet extraction of the impurities with petroleum ether (of boilingrange 6080C.) The residual material of melting point 21 3-2l5C, gave thefollowing elemental analysis by weight:

Required for CmHaTNHH- O Found Carbon 64.12% 64.01% Hydrogen 10.58%10.42% Nitrogen 22.44% 22.21%

Prolonged heating in vacuo of this compound afforded the anhydrousmaterial of melting point 217 219C.

EXAMPLE 6 8.19 Parts of the material prepared in Example 1 weredissolved in 60 parts of isopropanol and 9 parts of methyl iodide addedwith water cooling. After 120 hours a solid was separated by filtrationand washed with diethyl ether. The solid was dissolved in the minimumamount of water and sodium carbonate added until the solution was basic.Chloroform extraction afforded 2,4,6 tris[l,2,2,6',6'-pentamethylpiperidinyl-4'-oxy]-1,3,S-triazine. Thismaterial was crystallised from a 1:1 mixture of chloroform and ethanolto give a colourless solid of melting point 245-247C which gave thefollowing elemental analysis by weight.

Required |'o|'(':;il1,,..H,.() lollnd arhon 67.31% 67.36% Hydrogen10.27% 10.22% Nitrogen 14.27% 13.99%

EXAMPLE 7 25.8 Parts of 4-hydroxyl-2,2,6,6-tetramethylpiperidin-l-oxyland 8.4 parts of potassium hydroxide were dissolved in 500 parts ofwater. 9.2 parts of cyanuric chloride were carefully added and thesolution heated at reflux for 2hours. 5 Parts of a solid were filteredoff and washed with 20 parts of water followed by 20 parts of boilingpetroleum ether (boiling range -l00C). After drying this material2,4,6-tris[ l '-oxyl-2',2',6',6'-tetramethy1piperidinyl-4-oxy]-1,3,5-triazine, gave a melting point of192-194C and the following elemental analysis by weight:

Required for CMIHE NHO Found Carbon 60.97% 60.48%

Hydrogen 8.72% 8.56%

Nitrogen 14.22% 13.76%

EXAMPLE 8 14.75 Parts of cyanuric chloride were carefully added to amixture of 25 parts of 2,2,6,6-tetra methyl piperidin-4-ol and 13.5parts of sodium bicarbonate in 250 parts of water. The mixture wasstirred and heated to give a clear solution. After 6 hours a colourlessprecipitate had been produced which was filtered after cooling. Thesolid was washed three times with parts of water and dried in a vacuumoven to give 13.5 parts of 2-chloro-4,6-bis(2,2',6',6-tetra methylpiperidinyl-4-oxy)-1,3,5-triazine monohydrate. This material, of meltingpoint 225-226C, showed the following elemental analysis by weight:

Required for cg Hm N .-,O -(.I.H O Found Carbon 56.79% 56.50%

Hydrogen 8.63% 8.72%

Nitrogen 15.78% 15.71%

Chlorine 7.99% 7.86%

EXAMPLE 9 To 10.4 parts of 4-hydroxy-2,2,6,6-tetra methylpiperidin-l-oxyl in parts of dry benzene were added, in portions, 1.38parts of sodium. This mixture was heated at reflux for 18 hours and thencooled. 3.7 Parts of cyanuric chloride were added with care and themixture heated at reflux for 18 hours. On cooling the inorganic salt wasremoved by filtration and the filtrate evaporated in vacuo. Sublimationin vacuo of the residual solid removed unreacted 4-hydroxy-2,2,6,6-tetra methyl piperidin-l-oxyl and the residue was recrystallised threetimes from absolute ethanol to yield2-chloro-4,6-bis(1'-oxyl-2',2',6',6'-tetra methylpiperidinyl-4'-oxy)-1,3,5-triazine. This material had a melting point ofl97-199C and showed the following elemental analysis by weight:

Required for (T H .N.-,() .(1 Found Carbon 55.30% 55.24% Hydrogen 7.52%7.36% Nitrogen 15.36% 15.07% Chlorine 7.78% 8.01%

EXAMPLE To 4.94 parts of l-benzyl-2,2,6,6-tetra methyl piperidin-4-ol in100 parts of xylene were added, in portions, 0.8 parts of sodium. Thismixture was heated at reflux for 18 hours and then cooled. The excesssodium was removed and 1.2 parts of cyanuric chloride added with care.The mixture was stirred at reflux temperature for 3 hours. Evaporationof the solvent in vacuo afforded a solid which was Soxhlet extractedwith petroleum ether (of boiling range 80l00C) to give 1.7 parts of apale yellow solid. column chromatography on silica afforded 2,4,6-tril-benzyl-2,2,6,6'-tetra methyl piperidinyl-4oxy)-l ,3,5-triazine. Thismaterial had a melting point of l25-129C and showed the requiredspectroscopic features (Infrared, Nuclear Magnetic ResonanceSpectroscopy and Mass Spectrometry).

EXAMPLE 1 l 4.8 Parts of 2-chloro-4,6-bis(2',2',6,6-tetra methylpiperidin-4-amino)-l,3,5-triazine were dissolved in a mixture of 300parts of toluene and 200 parts tertiary butyl alcohol with warming. Asolution of 4 parts of the sodium salt of 2,2,6,6-tetra methylpiperidin-4-ol in 40 parts toluene (as prepared in the above Examples)was added dropwise and the mixture heated at reflux for 18 hours.Evaporation of the solution and treatment of the residue with parts ofwater afforded 4 parts of a colourless solid which was filtered anddried in vacuo. This material, 2,4-bis[2',2',6',6-tetra methylpiperidinyl-4'-amino]-6-[2",2",6",6"-tetra methyl piperidinyl-4"-oxy]- l,3,5-triazine, was crystallised from methanol and water to give amelting point of 186.5 -l 875C and had the following elemental analysisby weight:

Required for Found C,,H,.N.O.CH,OH Carbon 64.52% 64.67% Hy 10.48% 10.14%Nitrogen 19.43% 19.34%

EXAMPLE l2 4 Parts of 2,4,6-tris[2',2,6',6'-tetra methylpiperidin-4'-amino]-1,3,5-triazine in 100 parts of isopropanol at 5Cwere treated with 6.4 parts of iodomethane. The mixture was allowed tostand at room temperature for 3 days. Evaporation in vacuo afforded aresidue which was treated with saturated sodium carbonate. Filtrationand drying in vacuo afforded a colourless solid which was shown byspectroscopic means to be a partially methylated material. This materialwas dissolved in 180 parts of isopropanol and treated with 4 parts ofiodomethane. The mixture was allowed to stand at room temperature for 3days. Evaporation in vacuo, followed by treatment with saturated sodiumcarbonate, afforded a colourless solid, 2,4,6-tris( l ,2,-2',6,6'-pentamethylpiperidinyl-4'-amino)-1,3,5-triazine, which wasfiltered and dried in vacuo. This material was column chromatographed onalumina and then recrystallised from methanol and water to give amelting point of 235-240C. The compound gave the following elementalanalysis by weight:

Required for CMH NWHQO Found Carbon 65.63% 65.36% Hydrogen 10.85% 10.53%

EXAMPLE 13 To 4.8 parts of 2-chloro-4,6-bis(2',2,6',6'-tetramethylpiperidinyl-4'-amino)-1,3,5-triazine in a mixture of 100 parts ofethanol and 20 parts of water were added 4 parts of4-(B-arninoethyl)-2,2,6,6-tetra methyl piperidine. The solution wasstirred at reflux for 8 hours and then evaporated in vacuo. The residuewas dissolved in 25 parts of chloroform and washed with 50 parts ofwater. The chloroform phase was dried and evaporated to yield 6.0 partsof a colourless solid 01 melting point C. This material was columnchromatographed on alumina to give 2,4-bis(2',2',6',6'- tetra methylpiperidinyl-4-amino)-6-(2",2",6",6"- tetra methylpiperidinyl-4"-ethylenamino)-l,3,5-triazine of melting point 9699C. Thissubstance showed the following elemental analysis by weight:

Required for C H NH Found Carbon 67.20% 66.57%

Hydrogen 10.75% 10.65%

Nitrogen 22.05% 21.56%

EXAMPLE 14 Required C H44N 302C Found Carbon 64.10%

Hydrogen 8.76% 8.94%

Nitrogen l3.83% 13.35%

EXAMPLE 15 5.6 Parts by weight of 2-(2',2',6',6'-tetra methypiperidinyl-4')ethyl alcohol and 1.4 parts by weight c sodium wereheated to reflux for 24 hours in 100 part by volume of toluene. To theresulting solution wer added over 20 minutes 1.8 parts by weight ofcyanuri chloride in 30 parts by volume of toluene, and the re fluxcontinued for 18 hours. The toluene was then re moved by distillationunder reduced pressure and th solid suspended in water, this wasextracted with ethe (3 X 50 parts by volume), and the combined extractdried over magnesium sulphate. The ether was It moved by distillationand the residue was triturate with petroleum ether to give a solid whichwas co lected by filtration, dissolved in 20 parts by volume ethylalcohol and reprecipitated by the addition of 10 pal-ts by Vlume ofwater.

Thlli was obtained pure 2,4,6-tris[2',2,6,6'-te ramethylpiperidinyl-4-ethylenoxy]1,3,5-triazim melting at 104-6 and having thefollowing element: analysis b weight:

27 Required ,..H. ...N,.t). Found Carbon 68.51% 68.54% Hydrogen 10.57%10.48% Nitrogen 13.31% 13.40%

EXAMPLE 16 1.8 Parts by weight of cyanuric chloride and 11.0 parts byweight of 2-(2',2',6',6'-tetramethylpiperidi nyl-4') ethylamine wereheated at 160 with stirring for 4 hrs. The resulting mass was cooled andthe oil decanted off, this was diluted with 100 parts by volume of waterand allowed to stand at room temperature for 24 hours. A solidprecipitate was filtered, dried, and recrystallised from ethyl acetate(50 parts by volume) to give pure2,4,6-trisl2',2',6,6'-tetramethylpiperidinyl-4ethylenamino]1,3,5-triazine, melting at 169 and having the followingelemental analysis by weight:

Required C HtHh-IN. Found ('arbon 68.85% 69.09%

Hydrogen 11.07% 11.16%

Nitrogen 20.07% 20.02%

EXAMPLE 17 Required for C,,H ,N,Cl .HCl Found Carbon 42.30% 42.56%Hydrogen 5.92% 6.00% Nitrogen 20.55% 20.61%

EXAMPLE 18 A solution of 7.4 parts by weight of2-(2',2',6,6'-tetramethyl piperidinyl-4') ethyl amine in 20 parts byvolume of toluene was added dropwise to a stirred solution of 1.85 partsby weight of cyanuric chloride in 80 parts by volume of toluene. Theresulting suspension was stirred at room temperature for 24 hours, andthe solid then collected by filtration and treated with a 10% solutionof sodium hydroxide in water for a further 12 hours.

The resulting solid was collected by filtration, washed repeatedly withwater until the aqueous washings were pH 6 7, dried at 60C., andpurified by reprecipitation from a chloroform solution by the additionof petroleum ether (boiling range 60 80C.) to give Z-chloro- 4,6-di[2',2',6',6'-tetramethyl piperidinyl-4'- ethylenaminol-l ,3,5-triazine,melting at 168C. and having the following elemental analysis by weight:

Required for C H ClN Found Carbon 62.5% 62.32% Hydrogen 9.7% 9.3%Nitrogen 7.4% 7.65% Chlorine 20.4% 20.45%

28 EXAMPLE 19 38 Parts of polypropylene were homogenised with 0.076parts of n-octadecyl-fi (4-hydroxy-3',5'-t-butylphenyl) propionate in akneading machine over a period of 3 minutes at 200C. 0.19 Part of theproduct of Example 5 was then added and homogenisation was continued foranother 7 minutes.

This composition was compression moulded into films of 0.1 mm. thicknessat 260C. for 6 minutes and the films so obtained were then quenched incold water.

A section measuring 44 X 100 mm. was separated from the 0.1 mm. annealedpolypropylene foil and exposed to light irradiation in a fademeterdevice consisting of a circular bank of 28 alternate sunlight andblacklight lamps. The sunlight lamps were 2 feet long, -watt fluorescentlamps characterised by a peak emission of 3,100 Angstrom units; theblacklight lamps 20 were 2 feet long, 20-watt ultra-violet lampscharacterised by a peak emission of 3,500 Angstrom units.

The sample was rotated concentrically about the bank of lamps so thatthe radiation thereupon was uniformly distributed over the section undertest.

The exposed sample was examined periodically and portions of it testedto determine the percentage elongation at break, the time (T) at whichthe sample reached 50% of the initial elongation at break being noted.

A similar test was carried out on a polypropylene sample containing nostabiliser of the invention.

The results obtained are set out in the following Table:

TABLE Factor T/To Time to 50% of initial elongation at breakfl) Ex.Additive (additive) Time to 50% of initial elongation at break forcontrol (To) None 1 l9 2,4,6-Tris(2,2',6',6'- 3.5 45 tetramethylpiperidinyl-4'-amino)- 1,3,5-triazine EXAMPLE 20 5.6 parts of2-ethylamino-4,6-dich1oro-1,3,5-triazine was slurried in 300 parts ofwater and the mixture heated to a temperature of C. 4.8 parts of4-amino- 2,2,6,6-tetramethylpiperidine were then added followed by 30parts of 1N sodium hydroxide. The mixture was stirred at 55C. for sixhours. A colourless solid was then filtered off and washed with 700parts of warm water. 6.0 parts of Z-ethylamino-4-chloro-6-(2,2',6,6'-tetramethylpiperidinyl-4'- amino)-1,3,5-triazinewere obtained. This material had a melting point of 189 to 191C and gavethe following elemental analysis by weight:

Required for C H,,N,Cl Found Carbon 53.74% 53.55% Hydrogen 8.05% 7.96%Nitrogen 11.33% 11.38% Chlorine 26.86% 27.10%

EXAMPLE 21 Using identical conditions to Example 20, 6.2 parts of2-isopropylamino-4,6-dichloro-l,3,5-triazine were reacted with 4.8 partsof 4-amino-2,2,6,6-tetramethylpiperidine to yield 7 parts of2-isopropylamino-4- chloro-6-(2',2',6',6'-tetramethylpiperidinyl-4'-amino)-l,3,5-triazine. This substance had a melting point of 174 to 176Cand gave the following elemental analysis by weight.

Required for C H N CI Found Carbon 55.11% 54.85% Hydrogen 8.33% 8.04%Nitrogen 25.71% 25.95% Chlorine 10.85% 10.98%

EXAMPLE 22 Using identical conditions to Example 20, 6.7 parts of2-n-octylthio-4,6-dichloro-l,3,5-triazine were reacted with 3.55 partsof 4-amino2,2,6,6-tetrametl1ylpiperidine to yield 9.1 parts of2-n-octylthio-4-chloro- 6-(2',2',6,6'-tetramethylpiperidinyl-4'-amino)-l ,3 ,5- triazine. Thismaterial had a melting point of 79 to 81C and gave the followingelemental analysis by weight:

Required for C H N CIS Found Carbon 58.01% 57.86% Hydrogen 8.76% 8.73%Nitrogen 16.91% 16.89% Chlorine 8.56% 8.74% Sulphur 7.74% 7.44%

EXAMPLE 23 3.6 parts of 1,2,2,6,6-pentamethylpiperidin-4-ol were heatedwith 0.6 parts of sodium to reflux temperature in toluene. After 16hours the solution was cooled, the excess sodium removed and treatedwith 4.1 parts of 2-ch1oro-4,6-dimethylthio-l,3,5-triazine. The solutionwas heated at reflux temperature for 18 hours after which it was cooledand filtered free of sodium chloride. The solvent was evaporated underreduced pressure to yield a residue which was crystallised frompetroleum ether (of boiling point 6080C Two parts of2,4-dimethylthio-6-[ 1',2,2',6',6'-pentamethylpiperidinyl-4'-oxy]-l,3,5-triazine were obtained which showed a melting point of 143 to 145Cand gave the following elemental analysis by weight:

2.4 parts of 2-chloro-4,6-bis-[2',2,6',6'-tetramethyl-'piperidinyl-4'-amino]-l,3,5-triazine were treated with 1.2 parts ofisopropylamine in 40 parts of water. The solution was stirred at roomtemperature for 18 hours, at reflux temperature for four hours and thencooled and evaporated to yield 1.6 parts of material. This residue wastreated with parts of dilute sodium hydroxide and extracted twice with50 parts of chloroform. After drying and removal of the solvent asemi-solid material was obtained which on addition of two parts ofmetanol yielded a colourless solid 2-isopropylamino-4,6-bis-[2',2',6',6'-tetramethylpiperidinyl-4'-amino]- 1,3,5-triazine ofmelting point to 122C. It showed the following elemental analysis byweight:

Required for C H N Cl-l oH Found Carbon 62.72% 62.60%

Hydrogen 10.53% 9.98%

Nitrogen 23.42% 23.92%

EXAMPLE 25 0.36 parts of sodium were added to parts of ethanol and thesolution treated with 6.6 parts of 2-chloro-4,6-bis-[2',2,6',6'-tetramethylpiperidinyl-4-amino1- l,3,5triazine. Themixture was stirred and heated at reflux for 16 hours after which thesolution was cooled and filtered. Evaporation of the filtrate in vacuoafforded 6.6 parts of a colourless solid which was chromatographed on analumina column to yield 2-ethoxy-4,6-bis-(2',2',6,6-tetramethylpiperidinyl-4-amino)- l,3,5-triazine. Thismaterial has a melting point of 189 to 191C and gave the followingelemental analysis by weight:

Required for C H N O.H,O Found Carbon 61.40% 61 .4191

Hydrogen 10.05% 9.87%

Nitrogen 21.70% 21.46%

EXAMPLE 26 6.28 Parts of 4-amino-2,2,6,6-tetramethylpiperidine weredissolved in 100 parts of toluene and 4.1 parts of2-chloro-4,6-di(methylthio)-1,3,5-triazine were carefully added. Thesolution was stirred at reflux temperature for 6 hours. 6 Parts of asolid were filtered off and dried. This material was treated with 30parts of saturated sodium carbonate solution and extracted with 300parts of chloroform. The organic extract was dried and evaporated toyield a colourless tacky solid. Column chromatography on aluminaafforded pure 2-(2',2',6,6'tetramethylpiperidinyl-4-amino)-4,6-di(methylthio-l,3,5-triazine. This material was recrystallized from ethanol and had amelting point of 173 to 175C. It showed the following elemental analysisby weight:

Required for C H N S, Found Carbon 51.36% 51.63%

Hydrogen 7.70% 7.93%

Nitrogen 21.39% 21.45%

EXAMPLE 27 1.4 Parts of sodium and 6.28 parts of2,2,6,6-tetramethylpiperidin-4-ol was heated at reflux temperature for24 hours in 100 parts of toluene. To this cooled solution was added 3.86parts of 2-ethyl-amino-4,6- dichlorol ,3,5-triazine and the mixtureheated at reflux for 2 hours. Evaporation of the solvent in vacuoafforded a material which was extracted with chloroform using a Soxhletextractor. The extract was evaporated to yield a colourless solid whichwas chromatographed on an alumina column and then crystallised fromethyl acetate, to give pure 2-ethylamino-4,6-bis[2,2',6',6'-tetramethy1piperidinyl-4'-oxy]-1,3,5-triazine which showed a meltingpoint of l89.5 to 190.5 and the following elemental analysis by weight:

Required for C H N o, Found Carbon 63.54% 63.63%

Hydrogen 9.74% 9.77%

Nitrogen 19.34% 19.24%

EXAMPLE 28 3 Parts of2,4-dichloro-6-(2',2',6',6'-tetramethylpiperidinyl-4'-amino l ,3,S-triazine hydrochloric acid salt were dissolved in 400 parts of a 1;lmixture of ethanol and water. 1.18 Parts of n-propyl-amine were addedand the solution heated at reflux for 18 hours. Evaporation of thesolvent afforded a colourless solid which was crystallised from thesolvent mixture methanol/petroleum ether (of boiling range 60-80)\)/ethyl acetate to give pure 2-chloro-4-n-propyl-amino- 6-( 2',2',6,6'-tetramethy1piperidyl-4'-amino)-l,3 ,5- triazine hydrochloricacid salt of melting point greater than 270 and which gave the followinganalysis by weight:

Required for C,,H,,,N.Cl, Found Carbon 49.61% 49.26%

Hydrogen 7.77% 7.80%

Nitrogen 23.15% 22.54%

EXAMPLE 29 A solution of 2.1 parts by weight of 2-chloro-4,6-di(-methylthio)-1,3,5-triazine and 4.0 parts by wieght of 2( l,2,2,6',6'-pentamethylpiperidinyl-4 )-ethylamine in 50 parts by volumeof toluene was heated at reflux for 4 hours. The toluene was thenfiltered and removed by distillation under reduced pressure to give aresidual oil, which by trituration with petroleum ether (boiling range4060) gave a white solid. recystallisation from 25 parts by volume ofpetroleum ether (60-80) gave pure 2-(1,2',2',6',6-pentamethylpiperidinyl-4'-ethylenamino)-4,6-di(methylthio-1,3,5-triazine, melting at 1 19 andhaving the following elemental analysis by weight:

Required by C H N S, Found Carbon 55.27% 55.22%

Hydrogen 8.46% 8.62%

Nitrogen 18.96% 19.10%

Sulphur 17.32% 17.15%

EXAMPLE 30 1.5 Parts of2-chloro-4,6-bis[2',2',6',6'-tetramethylpiperidinyl-4'-amino]-1,3,5-triazinewere dissolved in 130 parts of an ethanol/water (:1 mixture and 4 partsof dimethylamine in ethanol solution (33%) added. The mixture was heatedin a rocking autoclave at a temperature of 100C and a pressure of 20atmospheres nitrogen for 24 hours. The solution was filtered and thefiltrate evaporated in vacuo to yield a pale brown solid. Charcoaltreatment of this material removed the colour and the product wasSoxhlet extracted with petroleum ether (of boiling range 60-80) for 24hours to yield 2-dimethylamino-4,6-bis[2,2',6',-6'-tetramethylpiperidinyl-4'-amino]-l ,3 ,5-triazine monohydrate as acolourless solid. It showed a melting point of 230 to 233C, a molecularweight of 432 by mass spectrometry and the following elemental analysisby weight:

Required for C H N,.H,O Found Carbon 61.92% 61.31%

Hydrogen 10.25% 10.28%

Nitrogen 24.62% 24.87%

EXAMPLE 31 3 Parts of2-chloro-4,6-bis[2',2',6',6'-tetramethylpiperidin-yl-4'-amino]-1,3,5-triazinewere dissolved in a mixture of 225 parts of ethanol and 46 parts ofwater with stirring and heating. 1.26 Parts of morpholine were added andthe solution heated at reflux for 24 hours. The solution was thenevaporated in vacuo and 50 parts of water added. After stirring for 30minutes the solution was filtered and the filtered material treated with50 parts of saturated sodium carbonate solution and extracted with 200parts of chloroform. The extract was dried and evaporated in vacuo toyield 2- morpholino4,6-bis[2',2,6',6'-tetramethylpiperidinyl-4'-amino]-l ,3,5-triazine dihydrate as a colourless solid of meltingpoint 179l 81C. This solid had a molecular weight of 474 by massspectrometry and showed the following elemental analysis by weight:

Required for C, H H O.21-l,0 Found Carbon 58.78% 58.60%

Hydrogen 9.87% 9.32%

Nitrogen 21.95% 22.06%

EXAMPLE 32 2.2 Parts of2-chloro-4,6-bis[2',2',6',6'-tetramethylpiperidiny1-4-amino]-1,3,5-triazineand 1.07 parts of benzylamino were heated at reflux in a mixture of 150parts of ethanol and 30 parts of water for 18 hours. An evaporation ofthe solvent, a material was obtained which was chromatographed on anAlumina column. Crystallisation from water gave 2-benzylamino-4,6-bis(2',2',6',6'-tetramethylpiperidinyl-4-amino]-1,3,5- triazinemonohydrate as a colourless solid of melting point 98 to 100C. It gavethe following elemental analysis by weight:

Required for C H N .H,O Found Carbon 65.60% 65.77%

Hydrogen 9.42% 9.40%

Nitrogen 21.82% 21.81%

EXAMPLE 33 2 Parts of2-chloro-4,6-bis[2',2',6',6'-tetramethylpiperidinyl-4'-oxy]-l,3,5-triazineand 248 parts of 4- amino-2,2,6,o-tetramethylpiperidine were heated atreflux with a mixture of 42 parts ethanol and 20 parts water for 18hours. A pure colourless solid was filtered from the solution which hada melting point of over 280C and a molecular weight of 406 by massspectrometry. This material was the hydrochloric acid salt of2-am'mo-4,6-bis[2,2,6,6'-tetramethylpiperidinyl- 4'-amino]-l.3,5-triazine and showed the following elemental analysis by weight:

Required for C, H ,.N,O,.HCl Found Carbon 56.92% 56.96% Hydrogen 5.87%8.71% Nitrogen 18.97% 19.28%

34 EXAMPLE 34 straightor branched alkyl of l to 20 carbon atoms, analkenyl or alkynyl of 3 to 12 carbon atoms, an aralkyl 3.6? t. f246-t'hlar g "c ompynmldme were dissolved havingfrom 7 to l 1 carbon atoms orthe group in a mixture of 12 parts of water and 20 parts of dioxane andthe solution stirred and cooled to C. 3 Parts 5 of4-amino-2,2,6,o-tetramethylpiperidine were then added slowly maintaininga temperature of below C. R,

0.8 Parts of sodium hydroxide in 2 parts of water were added and thesolution stirred at room temperature for l hour. 4.4 Parts of4-amino-2,2,6,6-tetrarnethylpiperi 10 dine were then added followed by0.8 parts sodium hydroxide in 2 parts of water. The resultant solutionwas then stirred at reflux temperature for 18 hours. A solid materialwas filtered off, treated with l00 parts of saturated sodium carbonatesolution and extracted with 200 parts of chloroform. The extract wasdried and wherein R9 is a hydrogen or alkyl of l to 20 carbon wherein Ris hydrogen, methyl or phenyl; n is O or 1; and A is CH or the groupevaporated to yield asolid,6-chloro-2,4-bis[2',2',6',6- atoms; Z" d Zare the same y P W f 'W l Q'Py or different and each is a piperidinegroup of formula ll monohydrate wh'ch was recrystallized from chlOrO- ashereinbefore defined, a halogen atom, a substituted form/petroleum ether(of boiling range 4060) to 20 amino group h vi th formula: give amelting point of l8 to 199.5C and the following elemental analysis byweight: Ill

wherein R and R are the same of different and each Required forC,,H,,N,CLH,O Found is hydrogen a straight or branched alkyl of l to 20car- 599m 59-63% bon atoms, a cycloalkyl of 5 to l2 carbon atoms, an

Hydrogen 9.37% 9.l 1% Nitrogen 905% 18.75% aryl WhlCh IS unsubstitutedor substituted with one or more alkyl groups and having a total of from6 to 18 carbon atoms or an aralkyl having from 7 to 12 carbon atoms, orR and R together with the nitrogen atom to l which they are bound, forma nitrogen containing ring c d f h f I having 5 to 7 ring atoms; or Z"and Z' are a hydroxy A compoun o t e a or an ether group having theformula:

OR, [V

2" wherein R, is hydrogen, a straight or brached chain alkyl of l to 20carbon atoms, a cycloalkyl of 5 to 12 carbon atoms, an aryl which isunsubstituted or substil tuted by one or more alkyl groups and having atotal of I 40 6 to 18 carbon atoms, or an aralkyl having from 7 to 12 Icarbon atoms; Z or Z" and Z are a thiol or thio ether group having theformula: and salts thereof, Z is a group having the formula:

wherein R, is hyrogen, a straight or branched alkyl of l to 20 carbonatoms or a cycloalkyl of S to 12 carbon CH atoms.

3 CH 2. A compound according to claim 1 having the for- 3 mula x (A nN-Y II D" L R N I N wherein R and R, are the same or different and eachis a straight or branched alkyl of l to 12 carbon atoms or D'" R and Rform together with the ring carbon atom to which they are bound, acycloalkyl group having from 50 5 to 12 carbon atoms;

and salts thereof, where D, D" and D' are the same or different and eachis halogen or a group of the formula:

CH X is -0, -S or -N, wherein 3 CH3 I y IIA :1 wherein R is hydrogen, astraightor branched alkyl of I R l to 20 carbon atoms or benzyl; Y is 0,hydrogen, a 1

wherein R, and R are the same or different and each is a straight orbranched alkyl of l to l2 carbon atoms,

Yll

or R, and R',, together with the carbon atom to which they are bound,form a cycloalkyl of 5 to 12 carbon atoms, X is an O, S0r R, wherein R,is hydrogen, an alkyl of l to 12 carbon atoms or an aralkyl of 7 to 12carbon atoms Y' is 0, hydrogen, an alkyl of l to 12 carbon atoms, analkenyl or alkynyl of 3 to 12 carbon atoms, an aralkyl of 7 to 12 carbonatoms or the group:

wherein R,, is hydrogen, or a methyl or phenyl, n is 0 or i and A isCH,, CH,CH,- or

wherein R, is an alkyl of l to 12 carbon atoms, with the proviso that atleast one of D, D" and D'" is not a halogen atom.

3. A compound according to claim 2, wherein X is O- or Nl-l, n is O, R,and R, are each methyl and Y is hydrogen or a methyl.

4. A compound according to claim 2, wherein D, D

5. A compound according the claim 1 having the formula:

H IC

RI 3 BN2 and salts thereof, wherein R", and R", are the same ordifferent and each is a straight or branched chain alkyl group havingfrom 1 to 12 carbon atoms or R", and R",, together with the carbon atomto which they are each bound, form a cycloalkyl of 5 to 12 carbon atoms,and Y", is hydrogen a straight or branched chain alkyl group having from1 to l2 carbon atoms, an alkenyl group having from 3 to 12 carbon atomsor an aralkyl group having from 7 to 12 carbon atoms 6. A compoundaccording to claim 5, wherein R", and R", are each methyl and Y" ishydrogen or a methyl.

40 7. A compound according to claim 1 which is 2,4,6-

5 1,3 ,5-triazine.

9. A compound according to claim 1 which is 2,4,6- tris-[ l'2',2',6,6pentamethylpiperidinyl-4-oxy]- 1,3 ,S-trizine.

10. A compound according to claim 1 which is 2,4,6-

I ,3,5-triazine.

11. A compound according to claim 1 which is 2- chloro-4,6-bis-[ l'-oxyl-2',2',6',6',-tetramethylpiperidinyl-4'-oxy]-l ,3,5-triazine.

and D are the same or different piperidine of formula "A- i i l

1. A COMPOUND OF THE FROMULA
 2. A compound according to claim 1 havingthe formula
 3. A compound according to claim 2, wherein X is - O- or-NH, n is O, R1 and R2 are each methyl and Y is hydrogen or a methyl. 4.A compound according to claim 2, wherein D, D and D are the same ordifferent piperidine of formula IIA.
 5. A compound according the claim 1having the formula:
 6. A compound according to claim 5, wherein R''''1and R''''2 are each methyl and Y'''' is hydrogen or a methyl.
 7. Acompound according to claim 1 which is 2,4,6-tris(2'',2'',6'',6''-tetramethylpiperidinyl-4''-oxy)-1,3,5-triazine.
 8. A compoundaccording to claim 1 which is 2,4,6-tris)2'',2'',6'', 6''-tetramethylpiperidinyl-4''-amino)-1,3,5-triazine.
 9. A compound according to claim1 which is 2,4,6-tris-(1''2'',2'',6'',6''-pentamethylpiperidinyl-4''-oxy)-1,3,5-trizine.
 10. A compoundaCcording to claim 1 which is2,4,6-tris-(1-oxyl-2'',2'',6'',6''-tetramethylpiperidinyl-4''-oxyl)-1,3,5-triazine.
 11. A compound according to claim 1 which is2-chloro-4,6-bis-(1''-oxyl-2'',2'',6'',6'',-tetramethyl-piperidinyl-4''-oxy)-1,3,5-triazine.